Chemical process and the product thereof



Patented July 21, 1942 I 2,290,582 FICE 2,290,583 CHEMICAL PROCESS AND THE PRODUCT THEREOF Emil Edward Dreger, Summit, iv. J., and John Ross, New York, N. Y., asslgnors to Colgate- Palmolive-Peet Company, Jersey City, N. corporation of Delaware No Drawing. Application September 2, 1939, Serial No. 293,220

13 Claims. (01. 260-408) This invention relates to the preparation of new organic materials and more particularly to the preparation of certain new halogen-containing organic sulphonates. I

It is an object of the present invention to prepare new, efllcient, detergent materials. It is also an object of this invention to prepare said materials by a convenient, economical process either in a batch or in a continuous manner. It is a further object of the present invention to prepare halogen-containing organic sulphonates which have excellent solubility and high washing efllciency in hot or cold, hard water, soft water and/or water containing appreciable quantities of dissolved material such as sea water.

' The present invention is directed to the preparation of compounds of the general formula (RO)mX(-Y)n wherein R is a halogen substituted alkyl or acyl radical having at least ten carbon atoms-preferably a halogen substituted saturated radical having at least fourteen carbon atoms and at least two halogen atoms; X is the residue of a polyhydroxy substance having at least one free hydroxy and/or halogen group; Y is'a hydrophilic radical of the type of acid,

sulphate, sulphonic acid, acid phosphate, acetate sulphonic acid and the corresponding salts thereof; m and n are small whole numbers.

It has been found that it is possible to prepare materials of the above type which have remarkable wetting, washing and emulsifyingwhen made into compounds of the present invention, such as monoglyceride monosulphates, produce materials having good deterging properties but their solubility is not as high as is often desired. Furthermore, when a more soluble monoglyceride monosulphate product is prepared from. the related unsaturated acids, such as oleic acid, the deterging efficiency is low. It has now been discovered that the presence of halogen substituents in the fatty acid molecule eflf ects an improved combination of deterging efllciency and solubility not previously attained with these unsubstituted long chain acids. It has further been found that the presence of at least two halogen atoms in the compounds produces materials having exceptional washing efliciency and solubility. Although the present invention is applicable to compounds having aliphatic chains of at least ten carbon atoms, these carbon chains advantageously contain between fourteen and twenty-two carbon atoms inclusive.

, It is a particular feature of the present invention to employ certain fatty acid materials which do not form especially efi'ective detergent materials and to convert them by the present process into highly desirable, detergent products.- -Unsaturated fatty acids, which are commonly found in various mixtures as free fatty acids or inthe form of their glycerides, produce monoglyceride monosulphates which have good solubility but not wholly satisfactory, deterging properties. If the unsaturated acids are converted into their corresponding saturated acids and then similarly made into monoglyceride monosulphate derivatives by the present process, the detergency is materially improved but the solubility of the compound is substantially depressed.

It has now been discovered that the halogenation of the fatty acids so as to replace the unsaturated linkages with halogen atoms and then converting the halogen-containing acid into an ester of a polyhydric alcohol sulphonate, either Relative washing efficiency Percent chlorine in tall oil of a 01% I lde monosulphate solution Per cent asses-e g It will be observed that at least 10% chlorine in the tall oil used in preparing the monoglyceride monosulphates will produce particularly eflicient materials. It'is preferred, however, to employ a' material in which substantially all the unsaturated groupings in the compounds have been removed by halogen and/or hydrohalcgen addition. a

The products of the present invention appear monoglycerto owe much of their eflectiveness to the preshalogen group or groups in the residue of the aliphatic polyhydroxy substance. The solubility, and the foaming. wetting and washing emciency seem to be intimately associated with the structure of the compound. Furthermore. this grouping containing hydroxy radicals seems to reduce materially the tendency of the products to dust when formed into powders, bubbles. flakes, ribbons. chips, or fibres; It is preferred to prepare the products fromglycerol. because this relatively inexpensive and abundant material is more eflicient and economical in preparing excellent products than one employing other polyhydrlc alcohols.

Although various hydrophilic groups may be attached to the polyhydroxy alkyl radical, it is preferred to prepare the acid sulphate or true sulphonate derivatives. It has been found that the acid sulphates are more easily prepared and possess more desirable physical properties.

The preferred products are advantageously prepared by mixin'gglycerine with oleum and then reacting the mixture with the halogencontaining fatty acid. The halogen-containing fatty acid and the glycerine are used in substantially equimolecular proportions. It is also possible to use a halogenated fatty oil or fat, in which case two mols of glycerine are used for each mol of oil or fat. A proportion of oleum is preferably selected that the concentration of the acid at the end of the reaction is not less than'about 99% sulphuric acid. This ensures substantially complete reaction to form halogencontaining fatty acid -monoglyceride monosule- The product is preferably neutralized in the presence of a large mass of previously neutralized material to prevent excessive rises in the pH value and to absorb thelarge heat of dilution and neutralization. The products may be rendered free from by-product salts by treatment with ethyl alcohol. butyl alcohol, acetone, carbitol, monoglycerides, Cellosolve. dioxane and/or the hire. It may also be accomplished by preparing the calcium salt and filtering the product from the insoluble calcium sulphate. The cation of a salt product of the present invention may be interchanged with the cation of an inorganic salt by treating a solution of one or more salts of the organic product in one or more of the above named solvents with an excess of a concentrated aqueous solution of a salt of that cation which is to be exchanged for the original organic product salt cation. It should be noted that any of the products falling within the scope of the present invention may be neutralized and purified by the above outlined procedure.

The above procedure is directed to the preparation of halogen-containing ester sulphates but it is also possible to prepare the corresponding ether sulphates. This is usually accomplished by reacting the long chain alcohol with the polyhydric alcohol or its derivative and then halo- .genating the ether formed. For example, oleyl alcohol is dissolved in xylene and finely divided sodamide added thereto until the evolution of ammonia ceases. Glycerine monochlorhydrin is then slowly added to the solution to form the glycerine mono-oleyl ether. The ether is separated from the xylene and treated withchlorine gas at about 20 C. while dissolved in a solvent such as carbon tetrachloride to yield the dichloroctadecyl ether of glycerine. The halogen-consalt.

taining ether may then be sulphated with oleum or the like, neutralized and treated as describedhereinbefore.

It is also possible to react an olefine halide such as allyl chloride with a sulphonating agent to form either a dichlor-propane sulphonic acid or a chlorhydroxypropane sulphonic acid and to react it with a halogen-containingfatty acid or soap thereof to form a halogen-containing fatty acid ester of a dilrvdroxypropane sulphonic acid or of a hydroxy-chlor-propane sulphonic acid.

The further treatment of this compound is substantially the same as previously described.

The following examples are given for the purpose of illustrating the present invention, but they are not to be construed as limiting on the scope thereof.

Example I To about 109 parts of 20% oleum are added about 11.3 parts of glycerol while the temperature is held 'at about 10 C. and the mix is stirred mechanically. After the glycerol is all added, the temperature is held at abozft 30 C. while about 41 parts of dichloroleic acid (21.1% C1) are added gradually. After two hours of agitation, the acid mixture is poured over 500 parts of ice and 500 parts of water and then neutralized with about 360 parts of 23.6% sodium hydroxide solution. This product is about 2.4 times as effective in washing as a similar product prepared from the corresponding non-chlorinated acid. In other words. its relative washing efficiency is about 240%. I

Example If About 7 parts of glycerol are added to about 54 parts of 20% oleum at about 10 C.-meanwhile stirring the mixture. After the glycerol is all added, the temperature is held at about 30 C.

while about 20 parts of monochlorpalrnitic acid (14.5% C1) are added gradually. After two hours of agitation, the acid mixture is poured over 250 parts of ice and 250 parts of water and then neutralized with about parts of 23.6% sodium hydroxide solution. To the neutralized solution is then added about an equal volume of butyl alcohol in order to extract the organic sulphate The alcohol is removed by distillation under vacuum to yield the final product. The washing efliciency of this product was excellent and the solubility as compared to corresponding non-halogenated acid was substantially improved.

Example III about 180 parts of 23.6% sodium hydroxide solution.

Other chlorinated tall oils having various chlorine contents were similarly prepared which were found to possess the relative washing efilciencies given hereinbefore.

Example IV parts of the sodium soap of chlorinated,

partially hardened, menhaden fish oil acids (22.6% C1) are reacted with 105 parts of the sodium salt of l chloro, 2 hydroxy propane, 3 sulphonic acid at about 150 C. for about 3 hours with vigorous agitation. The reaction products are dissolved in alcohol to separate sodium chloride therefrom. The purification of the product is completed by fractional crystallizations.

Example V About 13.0 parts of glycerol are added to about 109 parts of 20% oleum while the temperature is held at about C. and the mix is stirred mechanically. After the glycerol is all added, the temperature is held at about 30 C. while about 41 parts of chlorinated oleic acid (10.2% C1) are added gradually. After two' hours of agitation, the acid mixture is poured over 500 parts of ice and 500 parts of water and then neutralized with about 360 parts of 23.6% sodium hydroxide solution. This product is about 1.4 times as eifective in washing as a product prepared from the abietic acid (rosin), ricinoleic acid and naphthenic acids; and mixtures of these acids.

The preferred products are prepared by chlorinating the unsaturated acids obtained from black liquor or from fatty oils normally containing such fatty acids. 'For economical reasons, as well as because of the particularly desirable results, tall oil or liquid rosin is a most desirable raw material. Tall oil is a mixture of ingredients including fatty acids, resin acids and unsaponifiables such as phytosterols, which combination of incorresponding non-chlorinated acids, i. e., the

relative washing efiiciency is 140%.

Example VI To about 109 parts of 20% oleum are added about 11.5 parts of glycerol while the temperature is held at about 10 C. and the mix is stirred mechanically. After the glycerol is all added, the temperature is held at about 30 C. while about 41 parts of dichlorstearic acid (19.2% C1) are added gradually. After two hours of agitation,

the acid mixture is poured over 500 parts of ice and 500 parts of water and then neutralized with about 360 parts of 23.6% sodium hydroxide solution. To the neutralized solution is then added about an equal volume of butyl alcohol in order to extract the organic sulphate salt. The alcohol is removed by distillation under vacuum to yield the final product. A product of excellent washing efficiency is obtained which is much more soluble than a similar product prepared from the corresponding non-chlorinated fatty acid.

The chlorination of the fatty acids or oils used in the examples given above is conducted by treating the fatty material, directly or dissolved in a solvent such as carbon tetrachloride, with a stream of chlorine gas at a temperature as low as permissible. The vessel is usually immersed in a cooling bath during the reaction. When operatin with a solvent the temperature is usually about 20 C. and when operating without a solvent it is usually about 50 C. After a definite weight of chlorine has been passed in, the gas stream is stopped and the solvent removed by heating to about 50 C. while applying a vacuum. Although the above examples are directed to the preferred chlorine derivatives, it is also within the scope of this invention to prepare the corresponding bromine, iodine, and other halogenated or mixed halogenated derivatives. As mentioned hereinbefore, it is also possible toprepare the halogenated derivatives by addition of hydrohalides such as hydrogen chloride or hydrogen bromide to unsaturated linkages in the monoor poly-olefinic fatty acid or fatty alcohol chains.

The fatty acids which may be halogenated for use in the present invention include the saturated fatty acids such as stearic acid, palmitic acid, carnaubic acid, behenic acid, myristic acid, cerotic acid, melissic acid, eicosanoic acid, lauric acid, decanoic acid and the like; unsaturated fatty acids such as oleic acid, isoleic acid, linoleic acid, eleostearic acid, undecenoic acid, hexadecenoic acid, and the like; variuos other acid including gredients or variou parts thereof when used to prepare products of the present type produces a halogen-containing sulphonate mixture which has valuable properties different from many other related agents. The tall oil may be purified by fractional distillation, solvent extraction, fractional crystallization, air or steam blowing, brine washing of its soaps and/or treatment of its soaps in anhydrous state and in an inert atmosphere with steam at temperatures of the order of 200 C. to 350 C. to separate unsaponifiables therefrom. The tall oil may be separated into one or more of its components before being used or it may be used directly.

Other desirable sources of unsaturated acids are fish oils, including salmon oil, menhaden oil and shark oil; cottonseed oil, olive oil, soya bean oil, linseed oil, tung oil, rape seed oil, peanut oil, sunflower oil, and the like.

It is also possible to halogenate the fatty acid mixtures or the individual acids obtained from castor oil, palm oil, palm nut oihtallow, coconut oil. babassu nut oil, corn oil, sesame oil, wool fat, cocoa butter, cashew nut oil, cashew nut shell oil, oxidized petroleum, montan wax, spermaceti, whale oil, carnauba wax, or mixtures of any of the above listed fatty acids, fats, fatty oils, tall 2,279,734, issued April 14, 1942.

The polyhydric alcohols which may be used include glycerol, beta methyl glycerol, diglycerol, polyglycerols, cliand poly- (beta methyl glycerol), epichlorhydrin, glycerine chlorhydrin, 1,2,5-pentantriol; sugar alcohols such as mannitol, sorbitol, arbitol and erythritol; hydroxycarboxylic acids such as glyceric acid and sugar acids; and various mixtures thereof. Glycols, diglycols and polyglycols may be used along with the otherpolyhydric alcohols but alone they do not prove entirely satisfactory.

Among the sulphonating agents which are used to produce sulphonates or sulphates are sulphuric acid, oleum, acetyl sulphuric acid, glyceryl sulphuric acid, sulphuryl chloride, chlorsulphonic acid, bromsulphonic acid, sulphur trioxide and solutions of these agents in one or more solvents such as liquid sulphur dioxide.

The phosphating agents include phosphoric acid, pyrophosphoric acid, phosphorus oxychloride, phosphorus pentachloride. and phosphorus pentoxide.

It is also possible to prepare the esters of sulphocarboxylic acids, for example by preparing sodium sulphite. esters, such as the esters of sulphobutyric acid the mono-ester or acetate, andthen ether of glyceryl monochlorto react this material with Other sulphocarboxylic acid and the like, may be similarly prepared.

Although the new materials possess unusual deterging, sudsing, and water-softening properties by themselves, their action may be augmented by the addition of any of the common auxiliary agents used in soap and detergent compositions, Suitable addition agents are other emulsifying agents including soaps, rosinates, long chain alcohol sulphates, alkylated aromatic sulphonic acid salts, sulphonated mineral oil extracts, Turkey red oil, lecithin, glycerolamines, monoethanolamine, diethanolamine and triethanolamine; coloring matter such as dyes, lakes,

and pigments; abrasives and inert fillers such as silica, pumice, feldspar, precipitated chalk, infusorial earth, bentonite, talc, starch, and air; liquids including carbon tetrachloride, perchlorethylene, trichlorethylene, glycerine, ethyl alcohol, tetrahydrofurfuryl alcohol, phenol, cyclohexanol, water, tetralin, hexalin, pine oil, mineral oil, mineral oil extracts, andqiaphtha; perfumes and deodorants; -fats, oils, fatty acids, monoglycerides, vitamin F, waxes, gums, or resins, germicides such as phenol mercury chloride, phenyl mercury nitrate, phenyl mercury chloride, methyl salicylate and mercuric chloride; styptics; any of the common water-soluble salts such as sodium sulphate, chloride, acetate, bicarbonate, sesquicarbonate, hypochlorite, thiosulphate, hydrosulphite, and hyposulphate, or the corresponding ammonium and potassium salts thereof. The type of addition agent to be used, of course, will depend on the ultimate use of the new composition.

The water-soluble, water-softening compounds of tetraphosphoric, pyrophosphoric or hexametaphosphoric acid and their alkali metal, ammonia, and amine salts or alkyl esters may also be added to these compositions.

The final detergent composition with or without one or more addition agent may be formed into beads, flakes, bars, chips, crystals, powders, solutions, liquid or plastic emulsions, pastes, creams, salves, or any other forms desired. The ingredients maybe mixed by any of the common methods such as grinding, stirring, kneading, crutching, fusion, and drying by rolls, spray or otherwise of mixed solution.

The compositions may be used in washing compositions for wood, metal, stone, glass, brick, masonry and painted surfaces; insecticides; cements; abrasive compositions; antiseptics; water softeners; deodorants and disinfectants; water paints and polishes; sizes, glues and adhesives such as shellac and casein compositions; liquid, solid and paste tooth and mouth detergents; laundry detergents and other textile agents including laundry blueing, bleaching, dyeing, and discharging compositions; depilatories; dust preventing compositions; fire extinguishing compositions; drain, lavatory and radiator cleaners; anti-freezing, anti-fogging, and anti-corrosion compositions; wood impregnants; electrolytic baths; etching compositions; cosmetics, shaving preparations; shampoos and hair wave lotions; fat-liquors for leather; photographic solutions; plasticizers; paint, stain and grease removers; dry cleaning compositions; rug cleaners; petroleum de-emulsifying compositions; fruit washing; and any compositions requiring wetting,

washing, emulsifying, penetrating, soiubilizing, dispersing and like agents.

The presence of the halogen substituents in the new compounds of the present invention materially improves'the solubility of the compounds in solvents such as carbon tetrachloride, trichlorethylene, tetrachlorethane and various halogenated hydrocarbons, and consequently the products are particularly valuable as detergents in dry-cleaning operations.

As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that the applicants do not limit themselves to the specific proportions or embodiments thereof except as defined in the following claims.

We claim:

1. A polyhalogenated monocarboxylic acid partial ester of a polyhydric alcohol sulphonic acid salt.

2. A monoglyceride monosulphate of a polyhalogenated unsaturated fatty acid.

3. A polyhalogenated tall oil acid partial ester of a polyhydric alcohol partial sulphate.

4. A monoglyceride monosulphate of a ch10- rinated tall oil containing at least 10% chlorine.

5. The process of reacting a polyhydric alcohol having at least three functional groups selected from the class consisting of halogens and inrdroxy groups, with a sulphonating agentand a polyhalogen substituted carboxylic acid derivative.

6. The process of reacting a sulphonated polyhydric alcohol having ,at least two functional groups selected from the class consisting of halogens and hydroxy groups, with a polyhalogenated tall oil. I

7. A chemical compound represented by the general formula: (RO-)mX(-Y)n wherein X is the residue of an aliphatic polyhydroxy compound retaining at least one group of the class consisting of hydroxy groups and halogen groups; 0 is oxygen; R is a polyhalogen substituted lipophile carbon to carbon chain radical having at least ten carbon atoms, not more than one carboxyl group and joined to an oxygen on the residue of the aliphatic polyhyroxy compound through a group of the class consisting of ester and ether groups; Y is a hydrophilic radical of the class consisting of acid sulphates, sulphonic acids, acid phosphates, sulphomonocarboxylates, and the corresponding salts thereof; and m and n are small whole numbers.

8. A chemical compound as described in claim 7 wherein R is a polyhalogen substituted alkyl group having at least ten carbon atoms.

9. A chemical compound as described in claim '7 wherein R is a polyhalogen substituted lipophile acyl radical having at least ten carbon atoms.

10. A chemical compound as described in claim 7 wherein R is a dihalogen substituted lipophile acyl radical having at least ten carbon atoms.

11. A chemical compound as described in claim 7 wherein R is a polyhalogenated unsaturated acid radical having at least ten carbon atoms.

12. A chemical compound as described in claim '7 wherein R is a polyhalogenated resin acid radical having at least ten carbon atoms.

13. A chemical compound as described in claim 7 wherein R is a dihalogen substituted lipophile acyl radical having at least ten carbon atoms and Y is an acid sulphate salt,

EMIL EDWARD DREGER. JOHN ROSS. 

